Ultraviolet light absorbing agents and compositions and articles containing same

ABSTRACT

There are provided ultraviolet light absorbing agents of the formula ##STR1## wherein: X is &gt;C═O, or ##STR2## Y is H or OH; Z is H, OH, OQ or OW, where at least one Z is OH if Y is H; 
     Q is --CONH(CH 2 ) 3  Si(R 2 ) x  (OR 1 ) y  or --CONH(CH 2 ) 3  Si(R 2 ) x  (OCOR 1 ) y;  and 
     W is --C m  H 2m+1  ; 
     where x=0, 1 or 2, y=1, 2 or 3, x+y=3, R 1  and R 2 , independently, are each alkyl having 1 to 6 carbon atoms and m=1 to 18. Also provided are organopolysiloxane protective coating compositions containing said ultraviolet light absorbing agents having unique utility for protecting transparent plastic articles.

This is a division of application Ser. No. 154,621 filed May 30, 1981,now U.S. Pat. No. 4,321,400.

This invention relates to new, improved ultraviolet light absorbingagents, as well as to compositions containing such agents and toarticles coated with such compositions. The novel compounds of thisinvention are silanol-reactive alkoxysilyl- or alkanoyloxysilyl alkylcarbamyl adducts of aromatic ultraviolet absorbing agents.

BACKGROUND OF THE INVENTION

The use of transparent plastic materials in place of glass panels isbecoming more widespread. For instance, transparent glazing made ofsynthetic organic polymers is now employed more frequently intransportation, such as trains, buses and the like, in opticalequipment, and in contruction materials. In comparison with glass,transparent plastics are shatter-resistant and lighter in weight.

While enjoying the foregoing advantages, transparent plastics arenevertheless susceptible to scratching and marring on the surface, whichimpairs visbility and detracts from the physical appearance. Moreover,transparent plastics tend to undergo discoloration upon prolongedexposure to ultraviolet light, e.g., sunlight.

Attempts have been made to improve the abrasion resistance oftransparent plastics. It has been proposed, for instance, that mar- orscratch-resistant coatings for such plastics can be prepared frommixtures comprising silica and hydrolyzable silanes in a suitable mediumsuch an alcohol and water. Such protective coatings are described inMisch et al., U.S. Pat. No. 3,708,225, Clark, U.S. Pat. No. 3,986,997and U.S. Pat. No. 3,976,497, and Ubersax, U.S. Pat. No. 4,177,315. Otherscratch-resistant protective coatings are described in copendingcommonly assigned application Ser. No. 964,910, filed Nov. 30, 1978 andFrye, U.S. Pat. No. 4,277,287. Typically, these are applied to thesurface of the transparent plastic and heat cured in situ.

Attempts have also been made to reduce the tendency of the coatings ontransparent plastics toward deterioration on exposure to sunlight andthe like by incorporating in the coating compositions materials whichabsorb ultraviolet light rays. A disadvantage of many such ultravioletlight absorbing materials is that they often escape from thecompositions, e.g., by volatilization, usually during the heat curingcycle. Efforts to overcome this defect by using ultraviolet lightabsorbing materials having higher molecular weights, e.g., AmericanCyanamid's Cyasorb UV-531, have not been entirely successful.

Proskow, U.S. Pat. No. 4,051,161, discloses an alternative approach andthis is to use a silane-fluorohydroxy copolymer coating with asilanol-reactive functional derivative of an aromatic ultravioletlight-absorbing compound. As the agent to contribute thesilanol-reactive functional group it is proposed to use a complexepoxy-silane compound. The Proskow coating is not the preferred, lesscomplex silica-hydrolyzable silane coating of the earlier mentionedcitations. Other commonly assigned, concurrently filed applications alsodeal with functionalized uv screens. See Ashby et al., U.S. Pat. No.4,278,804; copending U.S. application Ser. No. 154,623 (Ching), filedMay 30, 1980; copending U.S. application Ser. No. 154,625 (Ching), filedMay 30, 1980; and U.S. application Ser. No. 154,626 (Ching), nowallowed, filed May 30, 1980 4,307,240.

The disclosures of the foregoing patents and applications areincorporated herein by reference.

It has now been discovered that reactive functional derivatives ofaromatic ultraviolet light-absorbing agents with superior properties inall important respects can be obtained by using alkoxysilylalkyl oralkanoyloxysilylalkylcarbamyl functional groups, and that these areuseful in the less complex systems, i.e., not the copolymer coatingsystems called for in U.S. Pat. No. 4,051,161.

With the new compounds of this invention scratch-resistant coatings fortransparent plastics can be made more resistant to discoloration uponexposure to ultraviolet light. Because such modified ultraviolet lightabsorbers are adapted to coreact with the polysiloxane of thescratch-resistant coating composition, there is a much reduced tendencyof such materials to escape or oxidize during thermal processing. Thisprovides substantial economy of use in comparison with the prior art.

DESCRIPTION OF THE INVENTION

According to this invention, there are provided new ultraviolet lightabsorbing agents having the following formula: ##STR3## wherein: Xis >C═O, or ##STR4## Y is H or OH; Z is H, OH, OQ or OW, where at leastone Z is OH if Y is H;

Q is --CONH(CH₂)₃ Si(R₂)_(x) (OR₁)_(y) or --CONH(CH₂)₃ Si(R₂)_(x)(OCOR₁)_(y) ; and

W is --C_(m) H_(2m+1) ;

where x=0, 1 or 2, y=1, 2 or 3, x+y=3, R₁ and R₂, independently, areeach alkyl having 1 to 6 carbon atoms, and preferably methyl and m=1 to18.

Within the foregoing class, the following compounds are preferred:##STR5## where Q is --CONH(CH₂)₃ Si(OCH₃)₃, --CONH(CH₂)₃ SiCH₃ (OCH₃)₂or --CONH(CH₂)₃ Si(CH₃)₂ (OCH₃). Special mention is made of the compound4-[γ-(trimethoxysilyl)propylcarbamoyloxy]-2,2',4'-trihydroxybenzophenone.

This invention also includes coating compositions comprising aneffective amount of the described ultraviolet light absorbing agents anda dispersion of colloidal silica in an aliphatic alcohol-water solutionof the partial condensate of a silanol having the formula RSi(OH)₃,where R is selected from the group consisting of alkyl having from 1 to3 carbon atoms and aryl, at least 70 percent by weight of the silanolbeing CH₃ Si(OH)₃. The dispersion contains from 10 to 50 percent byweight of solids, said solids consisting essentially of 10 to 70 percentby weight of colloidal silica and from 30 to 90 percent by weight of thepartial condensate. In most preferred embodiments, the dispersion has apH of from 7.1 to about 7.8.

The ultraviolet light absorbing agents of this invention can beprepared, for example, by a convenient method starting with a compoundhaving the formula ##STR6## in which X, Y and Z are as defined above. Inthis method the above compound is reacted in a solvent with anisocyanatopropylsilane having the formula OCN(CH₂)₃ Si(R₂)_(x) (OR₁)_(y)or OCN(CH₂)₃ --Si(R₂)_(x) (OCOR₁)_(y). R₁, R₂, X, and Y are definedabove. Of course, other methods will be obvious to those skilled in thisart.

The reaction of the isocyanatopropylsilanes and the phenolic compoundcan be run, generally, in the range of 50° to 150° C. for a period of 1to 6 hours. Yields of 85-98% are typical.

The isocyanatopropylsilanes for use in the above reaction are prepared,in good yield, by the platinum catalyzed reaction of an alkenylisocyanate with the corresponding alkoxysilyl hydride or acyloxysilylhydride. Alternatively, these are prepared by reacting alkenylisocyanatewith the corresponding chlorosilane followed by alkoxylation. Proceduresfor preparation of the foregoing are described in the literature, e.g.,by B. A. Ashby, in the Journal of Chemical and Engineering Data, 18, No.2, page 238 (1973), which is incorporated herein by reference.

The coating compositions of this invention are prepared by hydrolyzingan alkyltrialkoxysilane or aryltrialkoxysilane having the formulaRSi(OR)₃, where R is alkyl having 1 to 3 carbon atoms, or aryl,preferably phenyl, in an aqueous dispersion of colloidal silica toobtain a reaction product, and adding the described ultraviolet lightabsorbers to the resulting reaction product.

In general, the aqueous dispersion of colloidal silica is characterizedby a particle size of from 5 to 150 millimicrons, and preferably from 10to 30 millimicrons average diameter. Such dispersion are known in theart. Commercially available materials include Ludox (DuPont) and Nalcoag(NALCO Chemical Co.). These are available in the form of acidic or basichydrosols. With regard to this invention, if the pH of the coatingcomposition is basic, then usually a basic colloidal silica sol ispreferred for use in the composition. On the other hand, colloidalsilicas which are initially acidic but which have been adjusted to bebasic can also be used. It has been found that colloidal silica having alow alkali content, e.g., less than 0.35% by weight as Na₂ O, provides amore stable coating composition, and these are preferred.

In preparing the compositions, the aqueous dispersion of colloidalsilica is added to a solution of a small amount, e.g., from 0.07 to 0.10percent by weight, of an alkyltriacetoxysilane in alkyltrialkoxysilaneor aryltrialkoxysilane. The temperature of the reaction mixture is keptin the range between 20° to 40° C., preferably below 25° C. A reactiontime of about six to eight hours is usually sufficient to react enoughof the trialkoxysilane such that the initial two-phase liquid mixturehas been converted to a single liquid phase in which the silica isdispersed. Hydrolysis is permitted to continue for a period of 24 to 48hours, depending on the desired final viscosity. As a rule, the longerthe time permitted for hydrolysis, the higher the final viscosity.

During the preparation of the coating compositions, the alkyltriacetoxysilane is employed to buffer the viscosity of the initialtwo-phase liquid reaction mixture, and also to regulate the hydrolysisrate. Preferred are those alkyltriacetoxysilanes in which the alkylgroup contains from 1 to 6 carbon atoms, and especially 1 to 3 carbonatoms. Methyltriacetoxysilane is the most preferred. Althoughalkyltriacetoxysilanes are preferred for use, it is to be understoodthat glacial acetic acid or other acids may be used instead. Such otheracids include organic acids, such as propionic, butyric, citric,benzoic, formic, oxalic, and the like.

After hydrolysis has been completed, the solids content of the coatingcomposition is adjusted by adding alcohol to the reaction mixture.Suitable alcohols include lower aliphatics, e.g., having 1 to 6 carbonatoms, such as methanol, ethanol, propanol, isoproanol, n-butyl alcohol,t-butyl alcohol, and the like, or mixtures thereof. Isobutanol ispreferred. The solvent system, i.e., mixture of water and alcohol,should contain from about 20 to 75 percent by weight of the alcohol toensure that the partial siloxanol condensate is soluble.

Optionally, additional water-miscible polar solvents, e.g., acetone,butyl cellosolve, or the like, can be included in minor amounts, usuallyno more than 20 percent by weight of the solvent system.

After adjustment with solvent, the coating composition preferably had asolids content of from about 18 to about 25 percent by weight,especially preferably about 20 percent by weight of the totalcomposition.

The coating composition has a pH of from about 3.5 to about 8,preferably from about 7.1 to about 7.8, and especially preferably fromabout 7.2 to about 7.8. If necessary, a base, such as dilute ammoniumhydroxide, or weak acid, such as acetic acid, is added to adjust the pHwithin this range.

The silanetriols, RSi(OH)₃, are formed in situ as a result of admixingthe corresponding trialkoxysilanes with the aqueous medium, i.e., theaqueous dispersion of colloidal silica. Examples of the trialkoxysilanesare those containing methoxy, ethoxy, isopropoxy and n-butoxysubstituents which, upon hydrolysis, generate the silane-triols andfurther liberate the corresponding alcohol, e.g., methanol, ethanol,isopropanol, n-butanol, and the like. In this way, at least a portion ofthe alcohol content present in the final coating composition isprovided. Upon generation of the hydroxyl substituents to form ##STR7##bonding occurs. This condensation, which takes place over a period oftime, is not exhaustive but rather the siloxane retains a quantity ofsilicon-bonded hydroxyl groups which render the polymer soluble in thealcohol-water solvent mixture. This soluble partial condensate can becharacterized as a siloxanol polymer having at least one silicon-bondedhydroxyl group for every three ##STR8## units.

The portion of the coating composition which consists of non-volatilesolids is a mixture of colloidal silica and the partial condensate (orsiloxanol) of a silanol. The major portion or all of the partialcondensate or siloxanol is obtained from the condensation of CH₃Si(OH)₃. Depending on the input of ingredients to the hydrolysisreaction, minor amounts of partial condensate can be obtained, e.g.,such as from the condensation of CH₃ Si(OH)₃ with C₂ H₅ Si(OH)₃ or C₃ H₇Si(OH)₃, of CH₃ Si(OH)₃ with C₆ H₅ Si(OH)₃, or mixtures of theforegoing. For best results, it is preferred to use onlymethyltrimethoxysilane (thus generating all mono-methylsilanetriol) inpreparing the coating compositions. In the preferred embodiments, thepartial condensate is present in an amount of from about 55 to 75percent by weight, (the colloidal silica being present in an amount offrom total weight of solids in the solvent comprising a mixture ofalcohol and water. The alcohol comprises from about 50% to 95% by weightof the solvent mixture.

The coating compositions completely cure to hard coatings at atemperature of about 120° C., without the necessity of a curingcatalyst. If milder curing conditions are desired, it is preferred toinclude a buffered latent condensation catalyst. Such catalysts areknown to those skilled in the art. Examples include alkali metal saltsof carboxylic acids, such as sodium acetate, potassium formate, and thelike, amine carboxylates, such as dimethylamine acetate, ethanolamineacetate, dimethylaniline formate, and the like; quaternary ammoniumcarboxylates, such as tetramethylammonium acetate,benzyltrimethylammonium acetate, and the like; metal carboxylates, suchas tin octoate; amines, such as triethylamine, triethanolamine,pyridine, and the like; and alkali hydroxides, such as sodium hydroxide,ammonium hydroxide, and the like. It should be noted that commerciallyavailable colloidal silicas, particularly those having a basic pH, i.e.,above 7, contain free alkali metal base, and alkali metal carboxylatecatalysts are generated in situ during hydrolysis.

The amount of the curing catalyst can vary widely, depending uponparticular requirements. In general, the catalyst is present in anamount of from about 0.05 to about 0.5 and preferably about 0.1 percentby weight of the total coating composition. Such compositions arecurable on the substrate within a brief period of time, e.g., from 30 to60 minutes, using temperatures in the range from about 85° to about 120°C. A transparent, abrasion-resistant coating results.

The ultraviolet light-absorbing reaction products of this invention areadded to the described coating composition before, during or afterhydrolysis, and also before or after addition of solvent to adjust thesolids. In preferred compositions, the ultraviolet light absorbingagents of this invention are used in amounts from about 1.0 to about25.0, preferably from 5.0 to 10.0 parts by weight per 100 parts byweight of said composition on a solids basis.

Other ingredients may also be added. Special mention is made ofpolysiloxane-polyether copolymers, which control flow and prevent flowmarks, dirt marks, and the like, on the coating surface. Such materialsalso increase the stress cracking resistance of the coating.

Preferred for use in this invention are liquid polysiloxane-polyethercopolymers having the following formula: ##STR9## wherein R' and R" aremonovalent hydrocarbons, R"' is lower alkyl, preferably alkyl having 1to 7 carbon atoms, a is at least 2, preferably 2 to about 40, b is from2 to 3, n is from 2 to 4, and x is at least 5, preferably 5 to 100.

By way of illustration, R' and R", independently, are alkyl, such asmethyl, ethyl, propyl, butyl, octyl, and the like; cycloalkyl, such ascyclohexyl, cycloheptyl, and the like; aralkyl, such as benzyl,phenylethyl, and the like; alkenyl or cycloalkenyl, such as vinyl,allyl, cyclohexenyl, and the like; and halogenated derivatives of any ofthe foregoing, such as chloromethyl, chorophenyl, dibromophenyl, and thelike. Illustratively, R"' is methyl, ethyl, propyl, butyl, isobutyl,amyl, and the like.

The preparation of the above polysiloxanepolyether copolymer isdescribed in U.S. Pat. No. 3,629,165, incorporated herein by reference.Suitable commercially available materials are SF-1066 and SF-1141, fromGeneral Electric Company, Mallinckrodt's BYK-300, Union Carbide's L-540and Dow-Corning's DC-190.

Other ingredients, such as thickening agents, pigments, dyes, and thelike, can also be included for their conventionally employed purposes.These are added to the compositions after hydrolysis has been completed.

The coating compositions can be applied to the primed surface of anarticle using conventional methods, e.g., as by flow coating, sprayingor dip coating, to form a continuous film or layer thereon. The curedcompositions are useful as protective coatings on a wide variety ofsurfaces, either transparent or opaque, including plastic surfaces andmetal surfaces. Examples of such plastics include synthetic organicpolymeric substrates, such as acrylic polymers, e.g.,poly(methylmethacrylate), and the like; polyesters, e.g., poly(ethyleneterephthalate), poly(butylene terephthalate), and the like; polyamides,polyimides, acrylonitrile-styrene copolymers;styreneacrylonitrile-butadiene terpolymers; polyvinyl chloride;butyrates; polyethylene, and the like.

Special mention is made of the polycarbonates, such as thosepolycarbonates known as LEXAN®, available from General Electric Company,including transparent panels made of such materials. The compositions ofthis invention are especially useful as protective coatings on theprimed surfaces of such articles.

Suitable substrates also include both bright and dull metal surfaces,such as aluminum or sputtered chromium alloys. In addition, the coatingcompositions of this invention can be applied on other types of surfacessuch as wood, leather, glass, ceramics, textiles, and the like.

A hard coating is obtained by removing the solvent and other volatilematerials from the composition. The coating air-dries to a substantiallytack-free condition, but heating in the range of 75° C. to 200° C. isnecessary to obtain condensation of residual silanols in the partialcondensate. Final are results in the formation ofsilsesquioxane(RSiO_(3/2)). In the cured coating, the ratio ofRSiO_(3/2) units to SiO₂ ranges from about 0.43 to about 9.0, and moreusually from 1 to 3. A cured coating having a ratio of RSiO_(3/2) toSiO₂, where R is methyl, equal to 2, is most preferred. The coatingthickness can be varied, but, in general, the coating will have athickness in the range between 0.5 and 20 microns, more usually from 2to 10 microns.

The coating compositions described herein can be applied with goodadhesion to virtually any surface to provide protectively coatedarticles in accordance with this invention.

DESCRIPTION OF THE SPECIFIC EMBODIMENTS

The compounds, compositions and articles of this invention areillustrated in the following examples. All parts are by weight.

EXAMPLE 1

A solution of 24.6 parts of 2,2',4,4'-tetrahydroxybenzophenone in 95parts of N,N-dimethylformamide is prepared. To this solution is added20.5 parts of γ-isocyanotopropyltrimethoxysilane and a trace of stannousoctoate. The mixture is heated for one hour at 150° C. after which timeinfrared analysis records the absence of NCO absorption at 2280 cm⁻¹ andcompletion of the reaction. The solvent is removed by vacuumdistillation at 29 mm to a pot temperature of 99° C. There is obtained44.3 parts of a crystalline residue corresponding to 98% yield of##STR10##

Twenty-two and one-tenths parts by weight of Ludox LS silica sol(DuPont, an aqueous dispersion of colloidal silica having an averageparticle size of 12 millimicrons and a pH of 8.4), is added to asolution of 0.1 part by weight of methyltriacetoxysilane in 26.8 partsby weight of methyltrimethoxysilane. The temperature of the reactionmixture is kept at 20° to 25° C. The hydrolysis is allowed to continuefor 24 hours. The resulting reaction mixture has a solids content of40.5 percent. Isobutanol is added to bring the solids content to 20percent. The pH of the product is about 7.2.

The above compound and coating composition are mixed to form a singlecomposition which is flow-coated onto a transparent LEXAN®poly(bisphenol-A carbonate) panel which has been primed with athermosetting acrylic emulsion. The panel is air dried for 30 minutes,and then cured at 120° C. for one hour. After 500 Taber Abraser cycles(500 g. load, CS-10F wheels), according to ANSI-Z26.1-1977 section 5.17,the change in percent haze (Δ% H) is found to be 1.8. The sample passesthe cross-hatched adhesion test (DIN-53-151) after 7 days immersion inwater at 65° C. The sample also passes the cross-hatched adhesion testafter 1000 hours under R-S Lamp exposure on a rotating platform (3revolutions per minute), spaced 10 inches from the faces of an array of6 lamps arranged at 120° from one another.

In addition to the foregoing abrasion test results, it is observed thatthe coated panel does not discolor upon exposure to ultraviolet lightfor a period of 600 hours when tested by ASTM D 1925 on a HunterTristimulus colorimeter.

EXAMPLE 2

The procedure of Example 1 is repeated, except that 5 parts by weight ofSF-1066, General Electric Company, a polysiloxane-polyether copolymer,is included in the composition before coating. Substantially the sameabrasion resistance and ultraviolet absorbing properties in the curedcoating are obtained. In addition, the hard coating is smooth and clearand shows no signs of flow marks or stress cracking.

Other modifications and variations of the invention are possible in viewof the above disclosure. It is to be understood, therefore, that changesmay be made in the particular embodiments described without departingfrom the principles of the invention, and without sacrifice to the chiefbenefits.

I claim:
 1. An article comprising:(A) a substrate, (B) a primer layer onsaid substrate, and (C) a hard, protective coating over said primerlayer and said substrate, said coating comprising an aqueous compositionwhich comprises, before curing,(a) a dispersion of a colloidal silica ina solution of the partial condensate of a silanol having the formulaRSi(OH)₃, where R is selected from the group consisting of alkyl having1 to 3 carbon atoms and aryl, at least 70 weight percent of which is CH₃Si(OH)₃, in a mixture of an aliphatic alcohol and water, said dispersioncontaining from 10 to 50 percent by weight of solids, said solidsconsisting essentially of 10 to 70 percent by weight of the colloidalsilica and 30 to 90 percent by weight of the partial condensate, and`(b) an effective amount of an ultra-violet light absorbing agentcomprising a compound having the formula ##STR11## wherein: X is >C═O,or ##STR12## Y is H or OH; Z is H, OH, OQ or OW, where at least one Z isOH if Y is H; Q is --CONH(CH₂)₃ Si(R₂)_(x) (OR₁)_(y) or --CONH(CH₂)₃Si(R₂)_(x) (OCOR₁)_(y) ; and W is --C_(m) H_(2m+1) ; where x=0, 1 or 2,y=1, 2 or 3, x+y=3, R₁ and R₂, independently, are each alkyl having 1 to6 carbon atoms and m is 1 to
 18. 2. An article as defined in claim 1, inwhich the ultraviolet light absorbing agent is selected from the groupconsisting of: ##STR13## where Q is --CONH(CH₂)₃ Si(OCH₃)₃, --CONH(CH₂)₃SiCH₃ (OCH₃)₂ or --CONH(CH₂)₃ Si(CH₃)₂ (OCH₃).
 3. An article as definedin claim 2, wherein said ultraviolet light absorbing agent is4-[γ-(trimethyloxysilyl)propylcarbamoyloxy]-2,2',4'-trihydroxybenzophenone.4. An article as defined in claim 1, in which the aliphatic alcoholcomprises a mixture of methyl alcohol and isobutyl alcohol.
 5. Anarticle as defined in claim 1, which the silanol is CH₃ Si(OH)₃.
 6. Anarticle as defined in claim 1, in which the coating composition alsoincludes a polysiloxanepolyether copolymer. PG,24
 7. An article asdefined in claim 1, in which the colloidal dispersion in said coatingcomposition contains, before curing, from about 18 to about 25 percentby weight of solids consisting essentially of from about 25 to about 45percent by weight of the colloidal silica and from about 55 to about 75percent by weight of the partial condensate.
 8. An article as defined inclaim 1, in which the substrate comprises polycarbonate.
 9. An articleas defined in claim 8, in which the polycarbonate is transparent.